Method of making phenolic esters



Patented 1938 Glidden Company, cleveland ohio, a corpora tion of Ohio 'No Drawing. AppllcationAprll 2, 1935. e. 7 v -'14,376. Renewed March 26.11am;

10 Claims. ci. 260419;

I This application is a continuation in part of.- my

applications Serial #749,991, filed October'25, 1934, and Serial #1134 3, filed March 19, 1935.

This invention relates to the esterification of phenolic hydroxylgroups with high-boiling, relatively unreactive organic acids, and has particular reference to a new and novel method for conducting such esterifications whereby suchesters are obtained economically and successfully. In particular, it refers to a method of esterifying phe-. nolic hydroxyls with mixed, anhydrides of high and low-boiling acids. under such conditions that low-boiling acid is formed anddistilled Ofl, leaving an ester of the high-boiling" acid. v V

In the; production of phenyl esters, various methods havebeeri used. [Withthe active low molecularweight acids such as acetic acid,.the esters have been prepared by reacting the anhydride directly withgthe' phenol, in the presence of a condensing agent suchas caustic soda. 5 The f ester is then separated from thereactionmixture by any available method.

As the molecular weight of the acids increases, In the case of- ,,the straight chain saturated acids, this is particulartheir reactivity decreases.

1y true; and the anhydrides of acids with more than '1 carbon atoms (caprylic acid andhigher) will not esterify phenols by a simple direct reaction under normal operation conditions. It is necessary, in such cases, either torea'ct the phenols with the acid chloride, or to react themwith the acids in the presence of reagents which will form the acid chlorides in situ (e. g. phosphorous oxychloride, thionyl chloride). In either case,

hydrochloric acid is evolved; this (aid is extremely corrosive, and must be separated from the reac-.

tion mass. Furthermore, the acid' chlorides, and the carrying agentaare rather the commercial preparation of these esters is- 40 therefore not feasible. by this method. i It has been proposed-to esterify'phenols at extremely high temperatures with acid anhydrides; but, in addition to the difiiculties encountered in the reaction, it is extremely diflicult to separate the esters from the free acids liberated. In my application Serial #749,991, filed October 15, 1934, I have disclosed the fact that a phenolic resin containing free phenolic hydroxyl groups may be esterifled by mixing such a phenolic resin with a diflicultlyreactive acid, and a low-boiling organic acid anhydride, such as.acetic anhydride, and heating the-mixture in'such a manner that the free low-boiling acid formed is distilled oil, while the anhydride andhigh-boiling acid are kept in the reaction zone. In my coacid, and

expensive; and

pending application Isma #11343, med March 19, 1935, I 'have disclosed that this reaction is generic'for phenols. I 1 Ihavenow discovered that similar esters maybe prepared by'the action on a phenol of'a mix'edan 5 hydride'of a high-boiling and alow-boili ng car I boxylic acid; and that this reaction islikewise generic for all-phenolic hydroxylgroups whether I in freeph'en'ols'or in phenolic-resins.

By a higliboili'ngcarboxyliczacidisnieantin 10 the foregoing and in the claims sin-acid of this class which boils at above 200.'centigrade,at at-.

mospheric pressure. Examples offsuch acids are rosin, linseed oil and otheroil fatty acl srstearic benzoic acid. ,This is, of course, not a 15 a list of the acids I havefouncl tobe of w complete value;

By a low-boiling carboxylimacid' inthe foregoing and in the claimsis meant an-acidof this a class'-wrlch boils at below 190 centlgrade at at- 20.

mospheric pressure. Acetic acid is the acid of this} 1 class which has beenfoun'd to havethe greatest value, although propionic and chloroacetic acid are likewise available. l I I It; has beeen foundconvenient to preparethe 25,

mixed anhydrides by distilling low boiling car-j boxylic' acid'from a mixture of a'low-boiling acid anhydride and a high-boiling carboxylic acid.

Preferably one molecula'r weight. of the desired "high-boiling ,carboxylic acid and one mo- 30,

' lecular'weight'of the desired low boiling acid anhydride are placedin thevesseland oneniolecular I weight of thelow-bo'iling acid from 'which the anhydride is derived is distilled oiI while the'e'scape ofsubstantial amounts of the low-boilingan 35 hydride is prevented. Thislatter'maybe accom-== plished by theuse'of' asuitablqdis tilling column,

the design or which is [well known n' the arts.

To the mixedanhydride' so obtainedis added the phenol or, phenolic resin theJesterof which is 40 desired and low-boiling acid is again distllled fiqm. v

the mixture 'or solution. {This is-continued until -'the esteriflcationfis complete',, 'Offcourseg'itfis I obviousthat suflicient phenol orphenolresin must f; I I be addedto reactwith the mixedanhy'dride era 45 product having a high acid'nun b'er will result. If

I an excess'of a phenol is used; of course, freephen01 'willremain. This-can be removed by vacuuinf" distillation, or otherwise. If an excess ofphenolic resin'is used, a partial ester will result. Bypa'r- 50 tial ester ismeant one which containsin its composition unreacted or unesterified phenolic hydroxyl groups.

It'is important in the preliminary distillation j hich results .Iin the mixed 'anhydridesthat a 4 quantity of low-boiling acid not greatly exceeding one mol for each mol of low-boiling anhydride be distilled. If too much is distilled some excess anhydride of the high-boiling carboxylic acid will result. Since these anhydrides do not react readily or satisfactorily onaccountof the fact that by reaction they leavefree acid in the mass their formation should be avoided.

Specific examples will make clear the mode of operation, thus permitingthose skilled in the art to clearly understand the invention. It is to be understood that these examples are to be considered in a purely illustrative sense.

Example 1 In a vessel equipped suitable distilling column are added 239 parts of hydrogenated fish oil fatty acids and 90.5 parts of 95% acetic'anhydride. The solution is heated until 44 parts v of acetic acid have been distilled, the temperature at the top of the still head preferably not exceeding 120 centigrade. "To' the mixed anhydride are added IOO'grams of a cresylic acid inate tracesof acetic'acid anduncombinedphefraction boiling between 208 icentigrade and 215 eentigrade. The distillation is then continued until substantially all of, the acetic acid which canresult from the hydration of the acetic anhydride originally used 1 has been eliminated from'the reaction flask, The product is then" preferably subjected to reducedlp'ressur'e to elimnols.- Inthe final stages of the distillation at atmospheric pressureit is desirable, to raise 'the temperature of the reactants 280-290" centigrade.

-' Example 2 to approximately A mixture of 344 parts of rosin having an acid number of 163 and 110 parts of 92-95% acetic anhydride are heatedas above described until -63parts of acetic acid; have been distilled. To the mixed anhydride are added 105 parts of phenolic resin previously prepared from 100 parts of phenol and '12 parts of 40% formaldehyde in the presence of an acid catalyst and. by known methods.

Upon heating stantially all of theremainder of the acetic acid derivable from the aceticanhydride I has. been distilled. The product is substantially neutral,

. and soluble in oils.

It is advisable for most purposes to purify the "fester resin from traces of free acetic acid. {This may be easilyldon'e by subjectingthe resin to a reducedpressure while still hot. Any other suitable means may be usedt'o accomplishthe same In Example 2 the amount of mixedanhydride .used, is sumcient to substantiallycompletelyesterify all. the hydroxyl groups of the phenolic resin. Were a larger amount to .be used the final product would contain uncombined high-boiling carboxylic acid? in ,the formof its anhydride. When this is desirable'for any reason such excess may be used without departing frornthe spirit of this invention. When it is desired to esterify 'only a portion of the phenolichydroxylsa correspondingly smaller quantity'of the mixed anhydride'may be used. A partial ester will be formed in this case. r

It is apparent for the greatest, economy of materials that theflow-boiling anhydride should be used to anamount substantially equal molecularly to the high-boiling carboxylic acid. If an .be used to produce mixed esters.

a homogeneous solution is formed. The heating is continued until-subexcess of high carboxylic acid is used the phenyl or phenol resin ester will contain free high-boiling acid. When'this is not harmful or when it may be desired such an excess may be used'without departing from the spirit of this invention.

A convenientand economical method of preparing the mixed anhydrides has been here described. It is to be understood that other methnolic hydroxyl groups,

'While I have shown but one. example of a phenol, and one of a phenolic resin, and but one anhydride, it. is obvious that other low-boiling acid anhydridesIhigh-boiling acids and phenolic bodies may be used, without departnig from the spirit of my invention.

In the'cla'ims, the term heat treating is defined as heating under such conditions that the low-boiling acid derived from the anhydride is removed from thefreaction, while theoriginal reactantsare retained therein.

N01 claim is made. herein for the products resulting from the practice of this process. Such products are claimed in my cQ-pending applicatlon," Serial #749,991, above referred to.

"I-claiin:

1. The process of esterifyi a phenolic body containing free hydroxyl ';groups,. which comprises heating it,wi th a mixed anhydride of a "carboxylic'acid boiling below 190 C. and a carboxylic acid boiling above 200 C., to a tempera- Iture above the boiling point of the lower boiling 21 mm process of claim lfln which, the mixed v anhydride is suiiicient to completely esterlfy "all free phenolic hydroxyl groups with the car- 'boxylic acid boiling above 200 C.

V 3. The process of esterifying phenolic hydroxyls which comprises heating a phenolic body having free'hydroxyl groups with a mixed anhydride of a carboxylic acid boiling below 190 .C. and,a

*"carboxylic acid boiling above 200 C., to a temperature" above the boiling point of the lower boiling'acid, and distilling oi the lower-boiling acid as formed. I 1

4. The process of claim 3, in which the mixed anhydrideis-suflicient tocompletely esterify all free phenolic hydroxyl groups with the carboxylic' acid boiling above 200 C.

r 5. Theprocess of esterifying a phenolic body containing free hydroxyl groups which comprises heatingit with a mixed anhydride of acetic acid and acarboxylic acid boiling above 200to a temperature above the boiling point of acetic acid.

6. The process -of claim 5 in which the mixed anhydride is suillcient to completely esterii'y all free phenolic hydroxyl groups with the carboxylic acid boiling above. 200 C. Y

7. The process of esterifying a phenolic body containing free hydroxyl groups which comprises heating it with a mixed anhydride of aoeticacid and a carboxyllc acid boiling above 200 to a temperature above the boiling point of acetic acid;

v 8,184,888 and distilling of the acetic acid from the reac- I tion mixture as formed.

8. The process of claim 7 in which the mixed anhydride is sufiicient to completely esterify all free phenolic hydronl groups with the carboxylic acid boiling above 200 C.

9. The process of esterifying a phenolic body which comprises heating it with a mixed anhydride of acetic and oil fatty acids to a temperature above the boiling point of acetic acid, distilling oi! acetic acid from the reaction mixture as formed.

tilling of! acetic acid from the reaction mixture. 5 8

as formed, the mixed anhydride being present in such quantity that the high-boiling portion thereof is suiiicient'to completely esterify all free phenolic hydroxyl groups.

osoan A. mi, 

